JP2014153623A - Negative-type radiation-sensitive resin composition - Google Patents
Negative-type radiation-sensitive resin composition Download PDFInfo
- Publication number
- JP2014153623A JP2014153623A JP2013024738A JP2013024738A JP2014153623A JP 2014153623 A JP2014153623 A JP 2014153623A JP 2013024738 A JP2013024738 A JP 2013024738A JP 2013024738 A JP2013024738 A JP 2013024738A JP 2014153623 A JP2014153623 A JP 2014153623A
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- Prior art keywords
- resin composition
- group
- substrate
- sensitive resin
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims abstract description 39
- 230000005855 radiation Effects 0.000 title claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 32
- -1 polysiloxane Polymers 0.000 claims abstract description 27
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 20
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 15
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 9
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 claims abstract description 5
- RUFZNDNBXKOZQV-UHFFFAOYSA-N 2,3-dihydro-1h-pyrrolo[1,2-a]benzimidazole Chemical compound C1=CC=C2N(CCC3)C3=NC2=C1 RUFZNDNBXKOZQV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003505 polymerization initiator Substances 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 description 11
- 239000011521 glass Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 150000001343 alkyl silanes Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 125000005358 mercaptoalkyl group Chemical group 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 1
- PJQIBTFOXWGAEN-UHFFFAOYSA-N 1,2-dimethylbenzimidazole Chemical compound C1=CC=C2N(C)C(C)=NC2=C1 PJQIBTFOXWGAEN-UHFFFAOYSA-N 0.000 description 1
- TYMYJUHDFROXOO-UHFFFAOYSA-N 1,3-bis(prop-2-enoxy)-2,2-bis(prop-2-enoxymethyl)propane Chemical compound C=CCOCC(COCC=C)(COCC=C)COCC=C TYMYJUHDFROXOO-UHFFFAOYSA-N 0.000 description 1
- UCBVELLBUAKUNE-UHFFFAOYSA-N 1,3-bis(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)NC(=O)N(CC=C)C1=O UCBVELLBUAKUNE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OQZDJLFNMXRJHZ-UHFFFAOYSA-N 1-benzyl-2-ethylimidazole Chemical compound CCC1=NC=CN1CC1=CC=CC=C1 OQZDJLFNMXRJHZ-UHFFFAOYSA-N 0.000 description 1
- VQDKUWYOXTUWGQ-UHFFFAOYSA-N 1-benzyl-2-propan-2-ylimidazole Chemical compound CC(C)C1=NC=CN1CC1=CC=CC=C1 VQDKUWYOXTUWGQ-UHFFFAOYSA-N 0.000 description 1
- WIOWYXLFEJSLQR-UHFFFAOYSA-N 1-benzyl-2-propylimidazole Chemical compound CCCC1=NC=CN1CC1=CC=CC=C1 WIOWYXLFEJSLQR-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- CZAVRNDQSIORTH-UHFFFAOYSA-N 1-ethenoxy-2,2-bis(ethenoxymethyl)butane Chemical compound C=COCC(CC)(COC=C)COC=C CZAVRNDQSIORTH-UHFFFAOYSA-N 0.000 description 1
- HFCLUHMYABQVOG-UHFFFAOYSA-N 1-ethenyl-2-ethylimidazole Chemical compound CCC1=NC=CN1C=C HFCLUHMYABQVOG-UHFFFAOYSA-N 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 description 1
- SAYXNJMZYODLEQ-UHFFFAOYSA-N 1-ethenyl-2-propylimidazole Chemical compound CCCC1=NC=CN1C=C SAYXNJMZYODLEQ-UHFFFAOYSA-N 0.000 description 1
- IPNPFISPYWNXBR-UHFFFAOYSA-N 1-ethyl-2-methylbenzimidazole Chemical compound C1=CC=C2N(CC)C(C)=NC2=C1 IPNPFISPYWNXBR-UHFFFAOYSA-N 0.000 description 1
- SCZZNWQQCGSWSZ-UHFFFAOYSA-N 1-prop-2-enoxy-4-[2-(4-prop-2-enoxyphenyl)propan-2-yl]benzene Chemical compound C=1C=C(OCC=C)C=CC=1C(C)(C)C1=CC=C(OCC=C)C=C1 SCZZNWQQCGSWSZ-UHFFFAOYSA-N 0.000 description 1
- OLRZIJDZTTYZAP-UHFFFAOYSA-N 1-tributoxysilylethane-1,2-dithiol Chemical compound CCCCO[Si](OCCCC)(OCCCC)C(S)CS OLRZIJDZTTYZAP-UHFFFAOYSA-N 0.000 description 1
- VYZVLSZVMMTWDI-UHFFFAOYSA-N 1-triethoxysilylethane-1,2-dithiol Chemical compound CCO[Si](OCC)(OCC)C(S)CS VYZVLSZVMMTWDI-UHFFFAOYSA-N 0.000 description 1
- GFJLJZVUYNFQIR-UHFFFAOYSA-N 1-trimethoxysilylethane-1,2-dithiol Chemical compound CO[Si](OC)(OC)C(S)CS GFJLJZVUYNFQIR-UHFFFAOYSA-N 0.000 description 1
- OVXNVUKETMHHJA-UHFFFAOYSA-N 1-tripropoxysilylethane-1,2-dithiol Chemical compound CCCO[Si](OCCC)(OCCC)C(S)CS OVXNVUKETMHHJA-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- JHSWSKVODYPNDV-UHFFFAOYSA-N 2,2-bis(prop-2-enoxymethyl)propane-1,3-diol Chemical compound C=CCOCC(CO)(CO)COCC=C JHSWSKVODYPNDV-UHFFFAOYSA-N 0.000 description 1
- XXXFZKQPYACQLD-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl acetate Chemical compound CC(=O)OCCOCCO XXXFZKQPYACQLD-UHFFFAOYSA-N 0.000 description 1
- RFIMISVNSAUMBU-UHFFFAOYSA-N 2-(hydroxymethyl)-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC=C RFIMISVNSAUMBU-UHFFFAOYSA-N 0.000 description 1
- XVIYGQYAERBCSF-UHFFFAOYSA-N 2-(triethoxysilylmethyl)propane-1,3-dithiol Chemical compound CCO[Si](OCC)(OCC)CC(CS)CS XVIYGQYAERBCSF-UHFFFAOYSA-N 0.000 description 1
- IXDLODIQTOBRLW-UHFFFAOYSA-N 2-(trimethoxysilylmethyl)propane-1,3-dithiol Chemical compound CO[Si](OC)(OC)CC(CS)CS IXDLODIQTOBRLW-UHFFFAOYSA-N 0.000 description 1
- HYLSFDLHBABSIB-UHFFFAOYSA-N 2-(tripropoxysilylmethyl)propane-1,3-dithiol Chemical compound CCCO[Si](CC(CS)CS)(OCCC)OCCC HYLSFDLHBABSIB-UHFFFAOYSA-N 0.000 description 1
- KMZUNPOOESGZLF-UHFFFAOYSA-N 2-ethyl-1-methylbenzimidazole Chemical compound C1=CC=C2N(C)C(CC)=NC2=C1 KMZUNPOOESGZLF-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- QTGGAVCUIAYJHH-UHFFFAOYSA-N 2-triethoxysilylbutane-1,4-dithiol Chemical compound CCO[Si](OCC)(OCC)C(CS)CCS QTGGAVCUIAYJHH-UHFFFAOYSA-N 0.000 description 1
- XZXRTMQECSOELH-UHFFFAOYSA-N 2-trimethoxysilylbutane-1,4-dithiol Chemical compound CO[Si](OC)(OC)C(CS)CCS XZXRTMQECSOELH-UHFFFAOYSA-N 0.000 description 1
- GDTUHNUECXSHCK-UHFFFAOYSA-N 2-tripropoxysilylbutane-1,4-dithiol Chemical compound CCCO[Si](OCCC)(OCCC)C(CS)CCS GDTUHNUECXSHCK-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- ICHAUYNXFWOLPC-UHFFFAOYSA-N 3-tributoxysilylpropane-1-thiol Chemical compound CCCCO[Si](CCCS)(OCCCC)OCCCC ICHAUYNXFWOLPC-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- RHZAAYVDJRHENK-UHFFFAOYSA-N 3-triethoxysilylpropyl cyanate Chemical compound CCO[Si](OCC)(OCC)CCCOC#N RHZAAYVDJRHENK-UHFFFAOYSA-N 0.000 description 1
- DECHJJJXDGPZHY-UHFFFAOYSA-N 3-tripropoxysilylpropane-1-thiol Chemical compound CCCO[Si](CCCS)(OCCC)OCCC DECHJJJXDGPZHY-UHFFFAOYSA-N 0.000 description 1
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 1
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- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 1
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- 239000003963 antioxidant agent Substances 0.000 description 1
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- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012663 cationic photopolymerization Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical compound [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 1
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 1
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- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
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- 238000003618 dip coating Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
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- ZVJXKUWNRVOUTI-UHFFFAOYSA-N ethoxy(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OCC)C1=CC=CC=C1 ZVJXKUWNRVOUTI-UHFFFAOYSA-N 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 229940117360 ethyl pyruvate Drugs 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- BKXVGDZNDSIUAI-UHFFFAOYSA-N methoxy(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OC)C1=CC=CC=C1 BKXVGDZNDSIUAI-UHFFFAOYSA-N 0.000 description 1
- HSDFKDZBJMDHFF-UHFFFAOYSA-N methyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OC HSDFKDZBJMDHFF-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- HUZZQXYTKNNCOU-UHFFFAOYSA-N triethyl(methoxy)silane Chemical compound CC[Si](CC)(CC)OC HUZZQXYTKNNCOU-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Materials For Photolithography (AREA)
Abstract
Description
本発明は、ネガ型感放射線性樹脂組成物、及び該組成物から得られる樹脂硬化物並びに基板上に該組成物から得られるフィルムを形成した物品に関するものである。より詳細には、透明性及び硬度が高い樹脂硬化物を形成することができるネガ型感放射線性組成物、及び該組成物を硬化することにより得られる硬化物を有する物品に関する。 The present invention relates to a negative radiation-sensitive resin composition, a cured resin obtained from the composition, and an article in which a film obtained from the composition is formed on a substrate. More specifically, the present invention relates to a negative radiation-sensitive composition capable of forming a resin cured product having high transparency and hardness, and an article having a cured product obtained by curing the composition.
ＬＣＤ及び有機ＥＬを用いた画像表示装置や、タッチスクリーンパネルを用いた入力装置には、硬度が高く、かつ透明性の高い材料が求められている。タッチスクリーンパネルの構造は、ガラスまたはフィルム上にＩＴＯ（Ｉｎｄｉｕｍ ｔｉｎ Ｏｘｉｄｅ）及び金属で配線を作成し、金属絶縁膜や素子を保護するための保護膜が形成される。この保護膜は、高い硬度及び透明性を有しながら、基板との間の密着性、パターン形成のための感放射線性が求められる。 For an image display device using an LCD and an organic EL and an input device using a touch screen panel, a material having high hardness and high transparency is required. In the structure of the touch screen panel, a wiring is formed on glass or film with ITO (Indium tin Oxide) and metal, and a protective film for protecting the metal insulating film and the element is formed. The protective film is required to have high hardness and transparency, and adhesion to the substrate and radiation sensitivity for pattern formation.
硬度及び透明性の高い樹脂の一種として、不飽和結合を有する化合物とチオール基を有する化合物との反応（エン−チオール反応）を利用した硬化樹脂が知られている（特許文献１）。また、これを利用したパターン形成剤が知られている（特許文献２）。しかし、本発明者らの研究によれば、これらの文献に記載された化合物はＩＴＯ膜または配線を有する基板に対する密着性に劣ることがわかった。また、特許文献３には、同様のエン−チオール反応を利用した硬化樹脂にガラスとの接着性を良好にするために、接着促進剤としてシラン系化合物を含有することが記載されている。 As one kind of resin having high hardness and transparency, a cured resin using a reaction (ene-thiol reaction) between a compound having an unsaturated bond and a compound having a thiol group is known (Patent Document 1). Moreover, the pattern formation agent using this is known (patent document 2). However, according to studies by the present inventors, it has been found that the compounds described in these documents are inferior in adhesion to a substrate having an ITO film or wiring. Patent Document 3 describes that a cured resin using the same ene-thiol reaction contains a silane compound as an adhesion promoter in order to improve the adhesion to glass.
したがって、本発明の課題は、硬度・透明性を高く維持したまま、ＩＴＯ膜または配線を有する基板に対する密着性の高い硬化物が得られる感放射線性樹脂組成物を得ることにある。 Therefore, the subject of this invention is obtaining the radiation sensitive resin composition from which the hardened | cured material with high adhesiveness with respect to the board | substrate which has ITO film | membrane or wiring is obtained, maintaining hardness and transparency high.
本発明者らは、前記課題を解決すべく鋭意検討したところ、チオール基を有するポリシロキサン、多官能エチレン性不飽和化合物を含有する樹脂組成物に、特定の窒素含有化合物を添加することで、得られる硬化物の硬度・透明性を高く維持したまま、ＩＴＯ膜または配線を有する基板との間の密着性が向上することを見出し、本発明を完成した。 The present inventors diligently studied to solve the above problems, and by adding a specific nitrogen-containing compound to a polysiloxane having a thiol group, a resin composition containing a polyfunctional ethylenically unsaturated compound, The present invention was completed by finding that the adhesion between the obtained cured product and the substrate having the ITO film or wiring was improved while maintaining the hardness and transparency of the cured product high.
本発明の樹脂組成物を硬化して得られた樹脂は高い硬度及び高い透明性を維持しながら、ＩＴＯ膜または配線を有する基板上での高い密着性が得られる。 The resin obtained by curing the resin composition of the present invention has high adhesion on a substrate having an ITO film or wiring while maintaining high hardness and high transparency.
本発明のネガ型感放射線性樹脂組成物は、少なくとも１つのチオール基を含有するポリシロキサン、多官能エチレン性不飽和化合物、並びに一般式１及び一般式２からなる群から選択される少なくとも１つの窒素含有化合物を含有する。 The negative radiation sensitive resin composition of the present invention comprises at least one selected from the group consisting of polysiloxanes containing at least one thiol group, polyfunctional ethylenically unsaturated compounds, and general formulas 1 and 2. Contains nitrogen-containing compounds.
一般式１：
一般式１中、Ｒ１は水素原子、ビニル基またはベンジル基である。また、Ｒ２は水素原子又は炭素数１〜１１の直鎖又は分岐鎖のアルキル基を示す。
一般式１で表される化合物の例としては、イミダゾール、ビニルイミダゾール、Ｎ−ビニル−２−メチルイミダゾール、Ｎ-ビニル−２−エチルイミダゾール、Ｎ−ビニル−２−プロピルイミダゾール、Ｎ−ビニル−２−ウンデシルイミダゾール、Ｎ−ベンジル−２−メチルイミダゾール、Ｎ−ベンジル−２−エチルイミダゾール、Ｎ−ベンジル−２−プロピルイミダゾール、Ｎ−ベンジル−２−イソプロピルイミダゾールなどが含まれる。これらのうち、得られる樹脂組成物の安定性の観点から、特に好ましいものは下記式３で表されるビニルイミダゾール及び下記式４で表される１−ベンジル−２−メチルイミダゾールである。
In general formula 1, R 1 is a hydrogen atom, a vinyl group or a benzyl group. R 2 represents a hydrogen atom or a linear or branched alkyl group having 1 to 11 carbon atoms.
Examples of the compound represented by the general formula 1 include imidazole, vinyl imidazole, N-vinyl-2-methylimidazole, N-vinyl-2-ethylimidazole, N-vinyl-2-propylimidazole, N-vinyl-2. -Undecylimidazole, N-benzyl-2-methylimidazole, N-benzyl-2-ethylimidazole, N-benzyl-2-propylimidazole, N-benzyl-2-isopropylimidazole and the like are included. Of these, vinyl imidazole represented by the following formula 3 and 1-benzyl-2-methylimidazole represented by the following formula 4 are particularly preferable from the viewpoint of the stability of the obtained resin composition.
式３
式４
一般式２：
一般式２中、Ｒ１及びＲ２は各々独立して水素原子または炭素数１〜１１のアルキル基であり、Ｒ１とＲ２は互いに結合して環を形成してもよい。
一般式２で表される化合物の例としては、ベンズイミダゾール、１，２−ジメチルベンズイミダゾール、１−エチル−２−メチルベンズイミダゾール、１−メチル−２−エチルベンズイミダゾール、２，３−ジヒドロ−１Ｈ−ベンゾ[ｄ]ピロロ[１，２−ａ]イミダゾールなどが含まれる。これらのうち、下記式５で表される２，３−ジヒドロ−１Ｈ−ベンゾ[ｄ]ピロロ[１，２−ａ]イミダゾールが特に好ましい。
In General Formula 2, R 1 and R 2 are each independently a hydrogen atom or an alkyl group having 1 to 11 carbon atoms, and R 1 and R 2 may be bonded to each other to form a ring.
Examples of the compound represented by the general formula 2 include benzimidazole, 1,2-dimethylbenzimidazole, 1-ethyl-2-methylbenzimidazole, 1-methyl-2-ethylbenzimidazole, 2,3-dihydro- 1H-benzo [d] pyrrolo [1,2-a] imidazole and the like are included. Among these, 2,3-dihydro-1H-benzo [d] pyrrolo [1,2-a] imidazole represented by the following formula 5 is particularly preferable.
式５
本発明の樹脂組成物に用いられる窒素含有化合物は、一般式１及び一般式２からなる群から選ばれる化合物を１種のみ用いてもよいし、２種以上用いることもできる。 As the nitrogen-containing compound used in the resin composition of the present invention, only one compound selected from the group consisting of General Formula 1 and General Formula 2 may be used, or two or more types may be used.
本発明の樹脂組成物は、窒素含有化合物を樹脂組成物の固形分１００重量部あたり、０．１〜１０重量部含有することが好ましく、さらに好ましくは０．５〜３重量部である。窒素含有化合物の含有量が少ないと、密着増強作用が不十分であり、多すぎると、一液保管安定性（ポットライフ）が劣化し、塗布時の取り扱いが困難である。 The resin composition of the present invention preferably contains 0.1 to 10 parts by weight, more preferably 0.5 to 3 parts by weight of the nitrogen-containing compound per 100 parts by weight of the solid content of the resin composition. When the content of the nitrogen-containing compound is small, the adhesion enhancing action is insufficient, and when it is too large, the one-pack storage stability (pot life) is deteriorated and handling at the time of application is difficult.
本発明で用いられる、少なくとも１つのチオール基を含有するポリシロキサンは、１分子あたり１つ以上、好ましくは２つ以上のチオール基（メルカプト基ともいう）を含有する、シロキサンに基づく骨格を有する２次元又は３次元構造のオリゴマーまたはポリマーである。ポリシロキサンは、ケージ型構造、ランダム型構造またははしご型構造である。一般的にランダム型構造の方が容易に得られやすく、また放射線及び熱による硬化後の硬化物の硬度が高くなることから、好ましい。本発明で用いられるポリシロキサンは、好ましくは５００〜１０，０００の重量平均分子量を有し、さらに好ましくは、５００〜２，０００である。 The polysiloxane containing at least one thiol group used in the present invention has a siloxane-based skeleton containing one or more, preferably two or more thiol groups (also referred to as mercapto groups) per molecule. An oligomer or polymer having a three-dimensional structure. The polysiloxane has a cage structure, a random structure, or a ladder structure. In general, a random structure is preferred because it is easier to obtain and the hardness of the cured product after curing with radiation and heat is higher. The polysiloxane used in the present invention preferably has a weight average molecular weight of 500 to 10,000, and more preferably 500 to 2,000.
本発明で用いられる少なくとも１つのチオール基を含有するポリシロキサンの例は、（メルカプトアルキル）アルキルシランのオリゴマーまたはポリマー類（ホモポリマー及びコポリマーを含む）、メルカプト末端ポリシロキサンオリゴマー類、チオール基含有ポリシルセスキオキサン類などが含まれる。
好ましくは、本発明で用いられる少なくとも１つのチオール基を含有するポリシロキサンは、（メルカプトアルキル）アルキルシランのオリゴマーまたはポリマー類であり、オリゴマー及びポリマーはそれぞれモノマーの単独重合体及び他のモノマーとの共重合体を含む。（メルカプトアルキル）アルキルシランは、下記一般式（６）：
Ｒ１Ｓｉ（ＯＲ２）３
（式中、Ｒ１は少なくとも１つのチオール基を有する炭素数１〜８の炭化水素基、又は少なくとも１つのチオール基を有する芳香族炭化水素基を表し、Ｒ２は水素原子、炭素数１〜８の炭化水素基、または芳香族炭化水素基を表す。）で示される化合物である。
Examples of polysiloxanes containing at least one thiol group used in the present invention include (mercaptoalkyl) alkylsilane oligomers or polymers (including homopolymers and copolymers), mercapto-terminated polysiloxane oligomers, thiol group-containing polysiloxanes. Rusesquioxanes are included.
Preferably, the polysiloxane containing at least one thiol group used in the present invention is an oligomer or polymer of a (mercaptoalkyl) alkylsilane, and the oligomer and polymer are each a monomer homopolymer and other monomers. Including copolymers. (Mercaptoalkyl) alkylsilane has the following general formula (6):
R 1 Si (OR 2 ) 3
(In the formula, R 1 represents a hydrocarbon group having 1 to 8 carbon atoms having at least one thiol group, or an aromatic hydrocarbon group having at least one thiol group, and R 2 represents a hydrogen atom, having 1 to 1 carbon atoms. 8 represents a hydrocarbon group or an aromatic hydrocarbon group.).
（メルカプトアルキル）アルキルシランのオリゴマーまたはポリマーは、前記一般式（６）で示される化合物から誘導されるオリゴマーまたはポリマーであり、一般式（６）で示される化合物を加水分解及び縮合して得られる化合物を含む。（メルカプトアルキル）アルキルシランの例としては、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルトリエトキシシラン、３−メルカプトプロピルトリプロポキシシラン、３−メルカプトプロピルトリブトキシシラン、１，４−ジメルカプト−２−（トリメトキシシリル）ブタン、１，４−ジメルカプト−２−（トリエトキシシリル）ブタン、１，４−ジメルカプト−２−（トリプロポキシシリル）ブタン、１，４−ジメルカプト−２−（トリブトキシシリル）ブタン、２−メルカプトメチル−３−メルカプトプロピルトリメトキシシラン、２−メルカプトメチル−３−メルカプトプロピルトリエトキシシラン、２−メルカプトメチル−３−メルカプトプロピルトリプロポキシシラン、２−メルカプトメチル−３−メルカプトプロピルトリブトキシシラン、１，２−ジメルカプトエチルトリメトキシシラン、１，２−ジメルカプトエチルトリエトキシシラン、１，２−ジメルカプトエチルトリプロポキシシラン、１，２−ジメルカプトエチルトリブトキシシランなどがあげられ、オリゴマーまたはポリマーはこれらの単独または２以上の組み合わせから作成されることができる。これらの化合物のうち、３−メルカプトプロピルトリメトキシシランが特に好ましい。 The oligomer or polymer of (mercaptoalkyl) alkylsilane is an oligomer or polymer derived from the compound represented by the general formula (6), and is obtained by hydrolysis and condensation of the compound represented by the general formula (6). Contains compounds. Examples of (mercaptoalkyl) alkylsilane include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyltributoxysilane, 1,4-dimercapto-2 -(Trimethoxysilyl) butane, 1,4-dimercapto-2- (triethoxysilyl) butane, 1,4-dimercapto-2- (tripropoxysilyl) butane, 1,4-dimercapto-2- (tributoxysilyl) ) Butane, 2-mercaptomethyl-3-mercaptopropyltrimethoxysilane, 2-mercaptomethyl-3-mercaptopropyltriethoxysilane, 2-mercaptomethyl-3-mercaptopropyltripropoxysilane, 2-mercaptomethyl-3- Lucaptopropyltributoxysilane, 1,2-dimercaptoethyltrimethoxysilane, 1,2-dimercaptoethyltriethoxysilane, 1,2-dimercaptoethyltripropoxysilane, 1,2-dimercaptoethyltributoxysilane The oligomer or polymer can be made from these alone or in combination of two or more. Of these compounds, 3-mercaptopropyltrimethoxysilane is particularly preferred.
また、上記（メルカプトアルキル）アルキルシランに加えて、他のモノマーを用いて得られる共重合体も、本発明に用いることができる。他のモノマーの例としては、トリメチルメトキシシラン、トリメチルエトキシシラン、トリエチルメトキシシラン、トリエチルエトキシシラン、トリフェニルメトキシシラン、トリフェニルエトキシシランなどのトリアルキルアルコキシシラン類、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、メチルフェニルジメトキシシラン、メチルフェニルジエトキシシラン、３−メルカプトプロピルメチルジメトキシシランなどのジアルキルジアルコキシシラン類、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシランなどのアルキルトリアルコキシシラン類、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシランなどのテトラアルコキシシラン類、テトラメトキシチタン、テトラエトキシチタン、テトラプロポキシチタン、テトラブトキシチタンなどのテトラアルコキシチタン類、テトラエトキシジルコニウム、テトラプロポキシジルコニウム、テトラブトキシジルコニウムなどのテトラアルコキシジルコニウム類などの金属アルコキシド類を使用しうる。これら他のモノマーは、単独で、または２種以上を組み合わせて用いることができる。 In addition to the above (mercaptoalkyl) alkylsilane, a copolymer obtained using another monomer can also be used in the present invention. Examples of other monomers include trialkylalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Dialkyldialkoxysilanes such as diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, methyltrimethoxysilane, methyl Triethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyl Alkyltrialkoxysilanes such as triethoxysilane, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc. Metal alkoxides such as tetraalkoxytitaniums, tetraethoxyzirconium, tetrapropoxyzirconium, tetraalkoxyzirconium such as tetrabutoxyzirconium may be used. These other monomers can be used alone or in combination of two or more.
（メルカプトアルキル）アルキルシランのオリゴマーまたはポリマー類およびその製造方法、特に加水分解及び縮合によって製造する方法については、例えば、前記特許文献１または３に記載されており、当該記載に基づいて得ることができる。
本発明の樹脂組成物に用いられる少なくとも１つのチオール基を含有するポリシロキサンは、１種のみ用いてもよいし、２種以上用いることもできる。
The oligomer or polymer of (mercaptoalkyl) alkylsilane and the production method thereof, particularly the method of production by hydrolysis and condensation are described in, for example, Patent Document 1 or 3, and can be obtained based on the description. it can.
The polysiloxane containing at least one thiol group used in the resin composition of the present invention may be used alone or in combination of two or more.
本発明の樹脂組成物は、少なくとも１つのチオール基を含有するポリシロキサンを樹脂組成物の固形分１００重量部あたり、３０〜８０重量部含有することが好ましく、さらに好ましくは４０〜６０重量部である。当該化合物の含有量が少ないと、硬化後の膜の硬度が不十分であり、多すぎると、脆性が高く強度が不十分である。またチオール基の当量は後述する炭素二重結合の当量と同じか、これよりも低く調整することが好ましい。さらに好ましくはチオール：炭素−炭素二重結合のモル比が５０：５０から２０：８０の範囲である。チオールのモル比が大きすぎると未反応のチオールにより金属電極が腐食することが問題となり、小さすぎても充分な硬度が得られない。 The resin composition of the present invention preferably contains 30 to 80 parts by weight of polysiloxane containing at least one thiol group per 100 parts by weight of the solid content of the resin composition, more preferably 40 to 60 parts by weight. is there. When the content of the compound is small, the hardness of the film after curing is insufficient, and when it is too large, the brittleness is high and the strength is insufficient. The equivalent of the thiol group is preferably adjusted to be the same as or lower than the equivalent of a carbon double bond described later. More preferably, the molar ratio of thiol: carbon-carbon double bond is in the range of 50:50 to 20:80. If the molar ratio of thiol is too large, the problem is that the metal electrode is corroded by unreacted thiol, and if it is too small, sufficient hardness cannot be obtained.
本発明で用いられる多官能エチレン性不飽和化合物は、末端に炭素−炭素二重結合を有する化合物であり、アリル基、ビニル基、アクリル基、メタクリル基などの官能基を有する化合物が含まれうる。多官能エチレン性不飽和化合物の例としては、ジアリルフタレート、ジアリルイソフタレート、ジアリルシアヌレート、ジアリルイソシアヌレート、ペンタエリスリトールジアリルエーテル、ジアリルマレエート、ジアリルエーテルビスフェノールＡ、オルトジアリルビスフェノールＡなどのジアリル化合物；トリアリルイソシアヌレート、ペンタエリスリトールアリルエーテル、ペンタエリスリトールテトラアリルエーテル、トリメチロールプロパントリアリルエーテル、トリアリルトリメリテートなどのトリアリル化合物；ポリアリルポリエーテルポリオール、ポリアリルポリオールなどのポリアリル化合物；トリビニルイソシアヌレート、１−（ビニルオキシ）−２，２−ビス（（ビニルオキシ）メチル）ブタン、ポリビニルポリエーテルポリオール類などのビニル化合物；トリメチロールプロパントリアクリレート、トリメチロールプロパントリ（メタ）アクリレートなどのアクリル又はメタクリル化合物が含まれる。 The polyfunctional ethylenically unsaturated compound used in the present invention is a compound having a carbon-carbon double bond at the terminal, and may include a compound having a functional group such as an allyl group, a vinyl group, an acrylic group, or a methacryl group. . Examples of polyfunctional ethylenically unsaturated compounds include diallyl compounds such as diallyl phthalate, diallyl isophthalate, diallyl cyanurate, diallyl isocyanurate, pentaerythritol diallyl ether, diallyl maleate, diallyl ether bisphenol A, ortho diallyl bisphenol A; Triallyl compounds such as triallyl isocyanurate, pentaerythritol allyl ether, pentaerythritol tetraallyl ether, trimethylolpropane triallyl ether, triallyl trimellitate; polyallyl compounds such as polyallyl polyether polyol and polyallyl polyol; Nurate, 1- (vinyloxy) -2,2-bis ((vinyloxy) methyl) butane, polyvinyl polyether Vinyl compounds such as Le polyols; trimethylolpropane triacrylate, include acrylic or methacrylic compounds such as trimethylolpropane tri (meth) acrylate.
また、本発明で用いられる多官能エチレン性不飽和化合物は、２以上の官能基を有する化合物である。官能基は、上記アリル基、ビニル基、アクリル基、メタクリル基などを１分子中に２以上有していてもよいし、これらの官能基と、これら以外の官能基を有していてもよい。他の官能基としては、エポキシ基、チオール基、シアノ基などが含まれる。 Moreover, the polyfunctional ethylenically unsaturated compound used in the present invention is a compound having two or more functional groups. The functional group may have two or more of the above allyl group, vinyl group, acrylic group, methacryl group, etc. in one molecule, or may have these functional groups and other functional groups. . Other functional groups include epoxy groups, thiol groups, cyano groups, and the like.
本発明で用いられる多官能エチレン性不飽和化合物は、末端に炭素−炭素二重結合を有するものであれば、低分子化合物であっても、オリゴマーであってもよい。
本発明の樹脂組成物に用いられる多官能エチレン性不飽和化合物は、上記化合物を１種のみ用いてもよいし、２種以上用いることもできる。
The polyfunctional ethylenically unsaturated compound used in the present invention may be a low molecular compound or an oligomer as long as it has a carbon-carbon double bond at the terminal.
The polyfunctional ethylenically unsaturated compound used in the resin composition of the present invention may be used alone or in combination of two or more.
本発明の樹脂組成物は、多官能エチレン性不飽和化合物を樹脂組成物の固形分１００重量部あたり、２０〜７０重量部含有することが好ましく、さらに好ましくは４０〜６０重量部である。多官能エチレン性不飽和化合物の含有量が少ないと、硬化物の残膜率が不十分であり、多すぎると硬度が不十分である。 The resin composition of the present invention preferably contains 20 to 70 parts by weight, more preferably 40 to 60 parts by weight of the polyfunctional ethylenically unsaturated compound per 100 parts by weight of the solid content of the resin composition. When the content of the polyfunctional ethylenically unsaturated compound is small, the remaining film ratio of the cured product is insufficient, and when it is too large, the hardness is insufficient.
本発明のネガ型感放射線性樹脂組成物は、光重合開始剤を含有してもよい。光重合開始剤の種類は特に限定されず、従来公知の光カチオン重合開始剤、光ラジカル重合開始剤などから任意に選択できる。 The negative radiation sensitive resin composition of the present invention may contain a photopolymerization initiator. The kind of photoinitiator is not specifically limited, It can select arbitrarily from conventionally well-known photocationic polymerization initiator, radical photopolymerization initiator, etc.
光カチオン重合開始剤としては、スルホニウム塩、ヨードニウム塩、メタロセン化合物などを用いることができ、市販品としては、イルガキュア２６４（ＢＡＳＦ社製）、サンエイド Ｓａｎ・Ａｉ ＳＩ・１１０Ｌ（三新化学工業株式会社製）などがある。光カチオン重合開始剤の使用量は、樹脂組成物の固形分１００重量部あたり、０．０１〜１０ｇ、好ましくは０．０５〜１ｇである。 As the cationic photopolymerization initiator, sulfonium salts, iodonium salts, metallocene compounds, and the like can be used. As commercially available products, Irgacure 264 (manufactured by BASF), Sun-Aid San Ai SI. Etc.). The usage-amount of a photocationic polymerization initiator is 0.01-10g per 100 weight part of solid content of a resin composition, Preferably it is 0.05-1g.
光ラジカル重合開始剤としては、α・ヒドロキシアセトフェノン系、オキシムエステル系、アシルフォスフィンオキサイド系、チタノセン系などを用いることができ、市販品としては、イルガキュア１８４、イルガキュア３７９及びイルガキュア８１９（いずれもＢＡＳＦ社製）などがある。光ラジカル重合開始剤の使用量は、樹脂組成物の固形分１００重量部あたり、０．０１〜１０ｇ、好ましくは０．０５〜１ｇである。 As the radical photopolymerization initiator, α · hydroxyacetophenone, oxime ester, acylphosphine oxide, titanocene, and the like can be used. Etc.). The usage-amount of radical photopolymerization initiator is 0.01-10g per 100 weight part of solid content of a resin composition, Preferably it is 0.05-1g.
さらに、本発明のネガ型感放射線性樹脂組成物は、本発明の効果を損なわない範囲で、必要に応じて溶媒、安定剤、酸化防止剤、界面活性剤、シランカップリング剤などを配合してもよい。溶媒は、本発明のネガ型感放射線性樹脂組成物を基材上に形成する際に、該樹脂組成物を適切な粘度に調整するために使用することができる。溶媒の例としては、２−へプタノン、アセトン、メチルエチルケトン、１，１，１−トリメチルアセトンなどのケトン類；メタノール、エタノール、イソプロパノールなどのモノアルコール類；エチレングリコール、エチレングリコールモノアセテート、プロピレングリコールモノアセテート、ジエチレングリコールまたはジエチレングリコールモノアセテートのモノメチルエーテル、モノエチルエーテル、モノプロピルエーテル、モノブチルエーテルまたはモノフェニルエーテルなどの多価アルコール類及びその誘導体；ジオキサンのような環式エーテル類；乳酸エチル、酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル、ピルビン酸エチル、３−メトキシプロピオン酸メチル、３−エトキシプロピオン酸メチルなどのエステル類が挙げられ、これら溶剤は単独で用いても、２種以上を組み合わせて用いてもよい。 Furthermore, the negative radiation-sensitive resin composition of the present invention is blended with a solvent, a stabilizer, an antioxidant, a surfactant, a silane coupling agent, etc., as necessary, as long as the effects of the present invention are not impaired. May be. A solvent can be used in order to adjust this resin composition to a suitable viscosity, when forming the negative radiation sensitive resin composition of this invention on a base material. Examples of the solvent include ketones such as 2-heptanone, acetone, methyl ethyl ketone, and 1,1,1-trimethylacetone; monoalcohols such as methanol, ethanol and isopropanol; ethylene glycol, ethylene glycol monoacetate, propylene glycol mono Polyhydric alcohols such as acetate, diethylene glycol or diethylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; ethyl lactate, methyl acetate, Esters such as ethyl acetate, butyl acetate, methyl propionate, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate And the like, it is used those solvents alone or may be used in combination of two or more.
本発明のネガ型感放射線性樹脂組成物は、種々の方法、例えばディップコート法、スピンコート法、ロールコート法、スリットコート法などを用いて種々の基材の上に形成され、その後放射線照射、場合によってはさらに加熱され樹脂硬化物とすることができる。
放射線としては、紫外線光、Ｘ線、電子線などを用いることができ、これらは照射範囲、すなわち基材の面積によって選択する。例えば、紫外線を用いる場合は、５００〜３００ｎｍの紫外線を、２０〜５００ｍＪ／ｃｍ２で照射することにより、本発明のネガ型感放射線性樹脂組成物を硬化させることができる。
前記の放射線照射後に、さらに加熱することによって、より強固な樹脂硬化物を得ることができる。加熱条件としては対流式オーブンを用いた場合、１００〜３００℃で３０〜６０分、好ましくは１２０〜２３０℃で３０〜６０分である。
The negative radiation-sensitive resin composition of the present invention is formed on various substrates using various methods such as dip coating, spin coating, roll coating, and slit coating, and then irradiated with radiation. Depending on the case, it can be further heated to obtain a cured resin.
As the radiation, ultraviolet light, X-rays, electron beams and the like can be used, and these are selected according to the irradiation range, that is, the area of the substrate. For example, when ultraviolet rays are used, the negative radiation sensitive resin composition of the present invention can be cured by irradiating ultraviolet rays of 500 to 300 nm at 20 to 500 mJ / cm 2 .
By further heating after the radiation irradiation, a stronger cured resin product can be obtained. As a heating condition, when a convection oven is used, it is 30 to 60 minutes at 100 to 300 ° C, preferably 30 to 60 minutes at 120 to 230 ° C.
また、前記の放射線照射の際に、基材上に形成された樹脂組成物と放射線源との間にマスクを置きその一部に放射線を照射することによって、樹脂組成物の一部のみを硬化し、その後現像、熱硬化することによってパターンを形成することができる。現像液としては、テトラメチルアンモニウムヒドロキシド水溶液、水酸化ナトリウム水溶液または水酸化カリウム水溶液などを用いることができる。 In addition, during the radiation irradiation, a part of the resin composition is cured by placing a mask between the resin composition formed on the substrate and the radiation source and irradiating a part of the mask with radiation. Then, the pattern can be formed by subsequent development and heat curing. As the developer, a tetramethylammonium hydroxide aqueous solution, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, or the like can be used.
本発明のネガ型感放射線性樹脂組成物が形成される基材としては、ガラス、シリコン、プラスチック、セラミックス、金属、紙、布、木材などを含む種々の材料から得ることができる。本発明のネガ型感放射線性樹脂組成物から得られる硬化物は硬度及び透明性が高いため、ガラスまたはフィルム状のプラスチック基材、金属配線、半導体素子からなる基板上に硬化物を形成し、画像表示装置やタッチスクリーンパネルの入力構造の用途に最適に用いることができる。特に、本発明のネガ型感放射線性樹脂組成物から得られる硬化物はＩＴＯ基板との密着性が高いため、表面にＩＴＯ膜または配線が形成された基板を用いることが好ましい。 The substrate on which the negative radiation sensitive resin composition of the present invention is formed can be obtained from various materials including glass, silicon, plastic, ceramics, metal, paper, cloth, wood and the like. Since the cured product obtained from the negative radiation-sensitive resin composition of the present invention has high hardness and transparency, a cured product is formed on a substrate made of glass or a film-like plastic substrate, metal wiring, and a semiconductor element, It can be optimally used for an input structure of an image display device or a touch screen panel. In particular, since the cured product obtained from the negative radiation-sensitive resin composition of the present invention has high adhesion to the ITO substrate, it is preferable to use a substrate having an ITO film or wiring formed on the surface.
本発明のネガ型感放射線性樹脂組成物から得られる硬化物は、透明性及び硬度がたかく、さらにＩＴＯとの間の密着性が高いという特徴を持つ。
透明性は、ＵＶ・ＶＩＳ分光装置を用いて膜厚２ミクロンの硬化膜の透過率を測定することによって評価する。透過率が波長３６０ｎｍ以上の範囲で９８％以上であることが好ましい。また、硬度は、ＪＩＳＫ５６００・５・４に従って測定した鉛筆硬度で４Ｈ以上であることが好ましく、さらに好ましくは８Ｈ以上である。
The cured product obtained from the negative radiation-sensitive resin composition of the present invention is characterized by high transparency and hardness, and high adhesion to ITO.
Transparency is evaluated by measuring the transmittance of a cured film having a thickness of 2 microns using a UV / VIS spectrometer. The transmittance is preferably 98% or more in the wavelength range of 360 nm or more. Further, the hardness is preferably 4H or more, more preferably 8H or more in terms of pencil hardness measured according to JISK5600 · 5.4.
以下、本発明を実施例を用いて説明するが、本発明はこれらに限定されるものではない。なお、各実施例中の重量部は、樹脂組成物の固形物１００重量あたりの重量である。 EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to these. In addition, the weight part in each Example is the weight per 100 weight of solids of a resin composition.
実施例１
樹脂部の合計１００重量部に対して、チオール基を有するランダム型のポリシロキサン（荒川化学工業株式会社製「ＨＢＳＱ−１２７Ｂ」、重量平均分子量１，０００、チオール基当量１５０ｇ／Ｅｑ）を５５重量部、トリアリルイソシアヌレート（ＴＡＩＣ、日本化成株式会社製、商品名タイク、二重結合当量８３ｇ／Ｅｑ）を４５重量部、ビニルイミダゾールを０．５重量部、光重合開始剤としてイルガキュアＯＸＥ０１（以下ＩＲ−ＯＸＥ０１，ＢＡＳＦ社製）を０．１５重量部、安定剤として４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン１−オキシル（以下４−ヒドロキシＴＥＭＰＯ）を０．０１重量部、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）を固形分が３０重量パーセントとなるように加えた。室温で撹拌し、およそ３０分で全体が均一となった。
Example 1
55 weights of random polysiloxane having a thiol group (“HBSQ-127B” manufactured by Arakawa Chemical Industries, Ltd., weight average molecular weight 1,000, thiol group equivalent 150 g / Eq) with respect to 100 parts by weight of the resin part. Part, 45 parts by weight of triallyl isocyanurate (TAIC, manufactured by Nippon Kasei Co., Ltd., trade name, 83 g / Eq double bond equivalent), 0.5 part by weight of vinylimidazole, Irgacure OXE01 (hereinafter referred to as photopolymerization initiator) IR-OXE01, manufactured by BASF) 0.15 parts by weight, 0.01 parts by weight of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (hereinafter 4-hydroxy TEMPO) as a stabilizer, Propylene glycol monomethyl ether acetate (PGMEA) to a solid content of 30 weight percent The added. The mixture was stirred at room temperature, and the whole became uniform in about 30 minutes.
得られた樹脂組成物を、回転塗布法にて直径１５０ｍｍの白板ガラス基板および直径１５０ｍｍのシリコンウエハ上に直流スパッタ法にて取り付けたＩＴＯ膜付の基板に塗布した。塗布後は９０℃に加熱した熱板上で２分間、仮乾燥を行った。仮乾燥後の膜厚が１．８ミクロンとなるよう回転数を制御した。塗布膜の膜厚は光学干渉式の膜厚計（大日本スクリーン製造（株）製、ＶＭ２０３０）を用いた。 The obtained resin composition was applied to a substrate with an ITO film attached by a DC sputtering method on a white glass substrate having a diameter of 150 mm and a silicon wafer having a diameter of 150 mm by a spin coating method. After the application, temporary drying was performed for 2 minutes on a hot plate heated to 90 ° C. The rotation speed was controlled so that the film thickness after temporary drying was 1.8 microns. The film thickness of the coating film was an optical interference type film thickness meter (manufactured by Dainippon Screen Mfg. Co., Ltd., VM2030).
仮乾燥後の塗膜付基板を水銀灯光源により紫外線の照射を行った。水銀灯の強度は３６５ｎｍの輝線において２０ｍＷ／ｃｍ２とし、積算露光量が１００ｍＪ／ｃｍ２となるように基板の前面に露光した。 The substrate with the coating film after temporary drying was irradiated with ultraviolet rays using a mercury lamp light source. The intensity of the mercury lamp was 20 mW / cm 2 at an emission line of 365 nm, and the front surface of the substrate was exposed so that the integrated exposure amount was 100 mJ / cm 2 .
露光後の基板は２．３８重量％のＴＭＡＨ水溶液、マイクロポジットＴＭ ＭＦ ＣＤ−２６デベロッパー（ロームアンドハース電子材料社製）を用いて現像処理を施した。
現像はパドル法を用い、現像時間は６０秒間とした。現像後は脱イオン水にてリンス処理をし、次いで回転法により表面の水分を除去した。現像後の基板に焼成工程を施した。焼成温度は１２０℃とし、時間は６０分間とした。得られた白板ガラス基板及びＩＴＯ膜付きシリコンウエハ上の樹脂硬化物について、以下の手順に従い密着性測定を行った。
また、基板にガラス基板を用いた他は上記と同様の操作を行い、得られたガラス基板上の樹脂硬化物について、以下の手順に従い透明性及び硬度を測定した。
The exposed substrate was developed using a 2.38 wt% TMAH aqueous solution, Microposit TM MF CD-26 developer (Rohm and Haas Electronic Materials).
The paddle method was used for development, and the development time was 60 seconds. After development, the surface was rinsed with deionized water, and then water on the surface was removed by a rotation method. The substrate after development was subjected to a baking step. The firing temperature was 120 ° C. and the time was 60 minutes. Adhesion measurement was performed according to the following procedure for the obtained resin sheet on the white plate glass substrate and the silicon wafer with the ITO film.
Moreover, except having used the glass substrate for the board | substrate, operation similar to the above was performed and transparency and hardness were measured about the resin cured material on the obtained glass substrate in accordance with the following procedures.
＜測定方法＞
密着性
焼成後の基板はガラスカッターにより４分割した。分割後の基板を８０℃の温水中に浸漬した。浸漬時間は、無し、１時間および６時間とした。
浸漬処理後の基板の表面の水分を高圧窒素により除去後、１ｍｍ×１ｍｍの間隔でクロスカットを施した。クロスカット後の基板表面の切削屑を高圧窒素により除去後、ＡＳＴＭ Ｄ３３５９に準拠した方法で密着性を評価した。粘着テープにはＰ９９（ＰＥＲＭＡＣＥＬ社製）を用いた。密着試験後の試験片の表面を１０倍の光学顕微鏡（レーザーテック株式会社社Ｈ３００Ｍ）により観察し、その状態を同基準の標準チャートと比較して密着性を判定した。なお、判定結果５Ｂは粘着テープ剥離後にまったく樹脂の剥離が見られないもの、４Ｂは粘着テープ剥離後に樹脂の剥離が観察され、剥離面積がテープが貼られた全面積に対して５％未満のもの、３Ｂは同様に樹脂の剥離が５％以上１５％未満、２Ｂは樹脂の剥離が１５％以上３５％未満、１Ｂは樹脂の剥離が３５％以上６５％未満、０Ｂは樹脂の剥離が６５％以上のものである。
<Measurement method>
Adhesiveness The substrate after firing was divided into four by a glass cutter. The divided substrate was immersed in 80 ° C. warm water. The immersion time was none, 1 hour and 6 hours.
After removing the moisture on the surface of the substrate after the immersion treatment with high-pressure nitrogen, cross-cutting was performed at intervals of 1 mm × 1 mm. After removing the cutting scraps on the substrate surface after cross-cutting with high-pressure nitrogen, adhesion was evaluated by a method based on ASTM D3359. P99 (manufactured by PERMACEL) was used for the adhesive tape. The surface of the test piece after the adhesion test was observed with a 10 × optical microscope (H300M, manufactured by Lasertec Corporation), and the state was compared with a standard chart of the same standard to determine adhesion. In addition, the determination result 5B is the one in which no peeling of the resin is observed after the adhesive tape is peeled off, and 4B is the peeling of the resin after the adhesive tape is peeled off, and the peeled area is less than 5% with respect to the total area where the tape is stuck Similarly, 3B has a resin peeling of 5% to less than 15%, 2B has a resin peeling of 15% to less than 35%, 1B has a resin peeling of 35% to less than 65%, and 0B has a resin peeling of 65%. % Or more.
透過率
焼成後の塗布膜の厚さを前記の方法で測定後、可視紫外線分光測定装置（ベックマン社
製ＤＵ７０００）により塗膜の透過率を測定した。測定した透過率を膜厚が２ミクロンの場合に換算した値を透過率として比較した。３６０ｎｍの波長における透過率を評価した。
Transmittance After measuring the thickness of the coating film after firing by the above method, the transmittance of the coating film was measured with a visible ultraviolet spectrophotometer (DU7000 manufactured by Beckman). A value obtained by converting the measured transmittance when the film thickness was 2 microns was compared as the transmittance. The transmittance at a wavelength of 360 nm was evaluated.
硬度
ＪＩＳ Ｋ５６００−５−４に準拠した方法で硬度を評価した。ただし表面状態の確認は１０倍の光学顕微鏡写真（レーザーテック株式会社Ｈ３００Ｍ）より判定した。
Hardness Hardness was evaluated by a method based on JIS K5600-5-4. However, confirmation of the surface state was determined from a 10 × optical micrograph (Lasertec Corporation H300M).
実施例２
ビニルイミダゾールの量を表１に示す量に変更したこと以外は、実施例１と同様の操作を行い、得られた樹脂硬化物について各種評価を行った。結果を表１に示す。
Example 2
Except having changed the quantity of vinylimidazole into the quantity shown in Table 1, operation similar to Example 1 was performed and various evaluation was performed about the obtained resin hardened material. The results are shown in Table 1.
実施例３
重合開始剤をイルガキュアＯＸＥ０１からイルガュア３７９（以下ＩＲ−３７９，ＢＡＳＦ社製）に変更し、安定剤を４−ヒドロキシＴＥＭＰＯからハイドロキノンに変更した他は実施例１と同様の操作を行い、得られた樹脂硬化物について各種評価を行った。結果を表１に示す。
Example 3
The same procedure as in Example 1 was carried out except that the polymerization initiator was changed from Irgacure OXE01 to Irgure 379 (hereinafter IR-379, manufactured by BASF), and the stabilizer was changed from 4-hydroxy TEMPO to hydroquinone. Various evaluations were performed on the cured resin. The results are shown in Table 1.
実施例４−５
ビニルイミダゾールの代わりに、１−ベンジル−２−メチルイミダゾール（四国化成工業株式会社製 商品名「Ｂ２ＭＺ」）、２，３−ジヒドロ−１Ｈ−ベンゾ[ｄ]ピロロ[１，２−ａ]イミダゾール（四国化成工業株式会社製 商品名「ＴＢＺ」）をそれぞれ表１に示す量使用したこと以外は、実施例３と同様の操作を行い、同様に各種評価を行った。結果を表１に示す。
Example 4-5
Instead of vinylimidazole, 1-benzyl-2-methylimidazole (trade name “B2MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.), 2,3-dihydro-1H-benzo [d] pyrrolo [1,2-a] imidazole ( Shikoku Kasei Kogyo Co., Ltd. product name “TBZ”) was used in the same manner as in Example 3 except that the amounts shown in Table 1 were used, and various evaluations were similarly performed. The results are shown in Table 1.
実施例６
安定剤を入れなかった他は実施例１と同様の操作を行い、同様に各種評価を行った。結果を表１に示す。
Example 6
The same operation as in Example 1 was performed except that the stabilizer was not added, and various evaluations were performed in the same manner. The results are shown in Table 1.
実施例３で用いた４−ヒドロキシＴＥＭＰＯの構造
比較例１
ビニルイミダゾールを使用しなかったこと以外は、実施例１と同様の操作を行い、同様に各種評価を行った。結果を表２に示す。
Comparative Example 1
Except not using vinylimidazole, the same operation as Example 1 was performed and various evaluations were similarly performed. The results are shown in Table 2.
比較例２−５
ビニルイミダゾールの代わりに、１，３−ジアリル−５−（オキシラン−２−イルメチル）−１，３，５−トリアジン−２，４，６−トリオン（四国化成工業株式会社製 商品名「ＤＡ−ＭＧＩＣ」）、トリメトキシ（３−（オキシラン−２−イルメトキシ）プロピル）シラン（信越化学工業株式会社製 商品名「ＫＢＭ−４０３」）、（３−シアナトプロピル）トリエトキシシラン（信越化学工業株式会社製 商品名「ＫＢＭ−９００７」）、３−（トリメトキシシリル）プロパン−１−チオール（信越化学工業株式会社製 商品名「ＫＢＭ−８０３」）をそれぞれ表２に示す量で使用したこと以外は、実施例３と同様の操作を行い、各種評価を行った。結果を表２に示す。
Comparative Example 2-5
In place of vinylimidazole, 1,3-diallyl-5- (oxiran-2-ylmethyl) -1,3,5-triazine-2,4,6-trione (trade name “DA-MGIC, manufactured by Shikoku Kasei Kogyo Co., Ltd.) ], Trimethoxy (3- (oxiran-2-ylmethoxy) propyl) silane (trade name “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.), (3-cyanatopropyl) triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) Trade name “KBM-9007”), 3- (trimethoxysilyl) propane-1-thiol (trade name “KBM-803” manufactured by Shin-Etsu Chemical Co., Ltd.) in the amounts shown in Table 2, respectively. The same operations as in Example 3 were performed, and various evaluations were performed. The results are shown in Table 2.
比較例６
チオール基を有するポリシロキサンの代わりに、ポリエポキシアクリレート（分子量（１２，０００）、日本化薬株式会社製、商品名「ＺＦＲ-１４０１Ｈ」）を５５部用いた他は実施例１と同様の操作を行い、各種評価を行った。結果を表２に示す。
Comparative Example 6
The same operation as in Example 1 except that 55 parts of polyepoxyacrylate (molecular weight (12,000), manufactured by Nippon Kayaku Co., Ltd., trade name “ZFR-1401H”) was used instead of polysiloxane having a thiol group. And various evaluations were made. The results are shown in Table 2.
比較例２化合物（ＤＡ−ＭＧＩＣ）
比較例３化合物（ＫＢＭ−４０３）
比較例４化合物（ＫＢＭ−９００７）
比較例５化合物（ＫＢＭ−８０３）
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